Method for preparing detergent compositions



United States Patent '0 F 2,989,547 METHOD FOR PREPARING DETERGENT COMPOSITIONS 7 David D. Whyte, Wyoming, Ohio, assignor to The Procter & Gamble Company, Cincinnati, Ohio, a corporation of Ohio No Drawing. Filed Dec. 10, 1956, Ser. No. 627,131

6 Claims. (Cl. 260-648) This invention relates to a method for preparing detergent compositions.

More particularly, this invention relates to a method for preparing high molecular-alkyl glyceryl ether sulfonates.

Several methods for preparing alkyl glycenyl ether sulfonates are known. For the most part these call for the reaction of epichlorohydrin with high molecular weight alcohols in the presence of a suitable catalyst, the reaction product being most usually thealkyl monochloroglyceryl ether. In a co-pending application of D. D. Whyte and E. O. Korpi, Serial No. 659,038 filed May 1 4, 1957, which is a continuation-in-part of Serial No. 437,246 filed July 16, 1954 and now abandoned, a method has been disclosed for preparingalkyl glyceryl ether compounds through the reaction of an excess of epichlorohydrin with a high molecular weight alcohol, whereby alkyl poly chloroglyceryl ethers are formed along with the alkyl mono chloroglyceryl ethers. In all cases, the sulfonates of these ethers are formed through the normal Streckerization reaction, i.e. through treatment with sodium sulfite.

Alkyl glyceryl ether sulfonates prepared in accordance with the latter method described above have been found to have certain advantagesover those derived solely from alkyl monochlororglyceryl ethers (monomers). However, the method of preparation in the aforementioned co-pending application S.N. 659,038 results in the inclusion of a substantial amount of inorganic salt in the final alkyl glyceryl ether sulfonate product. When these alkyl glyceryl ether sulfonates are used for the preparation of various detergent products, difiiculties are encountered because of the high inorganic salt content. For example, when it is desired to prepare a detergent in bar form, the inorganic salt content of the alkyl glyceryl ether sulfonates makes it extremely difiicult to prepare a bar having a smooth surface. Inorganic salts can be removed by suitable extraction methods, but these are expensive and not well adapted for commercial practice.

In these previous methods for preparing the alkyl glyceryl ether sulfonates, moreover, the Streckerization reaction cannot be carried out successfully unless the total moisture content during Streckerization is at least about 50%. The presence of water in such amounts, which represents the minimum moisture consistent with good completeness in the Streckerization reaction, is apparently necessary because of the limited solubility of sodium sulfite, the Streckerization agent.

It is an object of this invention to provide a method for producing alkyl glyceryl ether sulfonates which have a low inorganic salt content and which are therefore eminently suitable for the preparation of the various detergent products in which inorganic salts have proved undesirable.

A further object of this invention is to provide a method for preparing alkyl glyceryl ether sulfonates through sulfonation of ethers at a moisture content below 50% with good completeness.

Other objects will become apparent from the following detailed description.

In general, the objects of this invention can be accomplished by forming an alkyl glyceryl ether through the reaction of a fatty alcohol with epich'lorohydrin, treating Patented June 20, 1961 the resulting alkyl glyceryl chloro ether with an aqueous alkali metal hydroxide solution to form the epoxlde of the ether product and then sulfonating the epoxidized ether product with alkali metal sulfite and alkali metal bisulfite in combination.

More specifically, the process of this invention comprises: reacting a fatty alcohol having from about 10 to about 20 carbon atoms with a molar excess of epichlorohydrin in an amount sufficient for the formation of an alkyl glyceryl ether product containing at least about 10% and not over about 30% by weight of alkyl diglyceryl dichloro ether; epoxidizing the said ether product by treating it with an aqueous alkali metal hydroxide solution having a concentration of from about 25% to about 50% at a temperature in the range from about 160 to about 300 F.; settling the epoxidized mixture, whereupon the mixture stratifies and the aqueous phase, which contains in solution the major portion of the inorganic salt formed during the epoxidation, settles out of the epoxidized ether phase; removing the epoxidized ether stratum and treating it with an aqueous solution comprising a mixture of sodium 'sulfite and sodium bi-sulfite proportioned to give a final pH in the range from about 5 to about 8.

Although the foregoing process has been described in terms of a batch-type operation, the process may be conveniently carried out in acontinuous manner, the stratifying operation being readily accomplished through centn'fugation. I

Wherever herein the term alky appears it is to be understood to include within its scope the alkenyls as well as the true alkyls. v I s The alkyl glyceryl chloro ether product is preferably prepared in accordance with theprocess disclosed the co-pending application of D. D. Whytc and E. O. Korpi, filed June 16, 1954, and bearing Serial Number 437,246, now abandoned. Therein, a high molecular weight @1- cohol is reacted with an excess of epichlorohydrin in the presence of a suitable catalyst to form alkyl chlo'roglyceryl ethers of the general formula H in Hdo -13.

where R represents an alkyl radical of from about 10 to about 20 carbon atoms and n is an integer from 1 to 4. As pointed out in that application, fatty alcohols having from 10-20 carbon atoms in the alkyl chain or mixtures thereof, as well as the oxo alcohols, can be readily used in the preparation of the alkyl glyceryl chloro ether product.

C fatty alcohols, has been found particularly suitable. T-hese fatty alcohols are normally reacted with about 5% or greater excess epichlorohydr'in so that at least 10% and not more than about 30% of alkyl di-glyceryl dichloro ether (dimer) is formed.

The ether product from the above mentioned reaction is treated in accordance with this invention with an aqueous solution of alkali metal hydroxidehaving a concentration from about 25% to about 50% to convert itto the glycidyl (epoxy) ether. Amounts of alkali metal hydroxide solution of the aforementioned concentrations from 0% to about 50% in excess of the stoichiometric amount needed to completely epoxidize allof the alkyl glyceryl chloro ethers present find ready applicationin the epoxidation reaction. j

This epoxidation is conveniently carried outat terr'iperatures in the range froni about to 200 F. under The middle cut of the fatty alcohols derived from coconut oil, i.e., the fraction containing largely C and 3 atmospheric pressure. However, temperatures in excess of 200 F., for example, as high as 300 F., can be used if the epoxidation is accomplished in an autoclave and certain precautions are taken, i.e., the time of epoxidation is reduced so that extensive hydrolysis of the epoxide will not take place.

In the previously known methods for preparing alkyl glyceryl ether sulfonates, Streckerization of the alkyl glyceryl chloro ethers utilizing sodium sulfite as the Streckerizing agent resulted in the inclusion in the final product of one mole of sodium chloride for each mole of combined epichlorohydrin. As has been pointed out hereinbefore, the presence of sodium chloride (inorganic salt) in appreciable quantities in the alkyl glyceryl ether sulfonate product gives rise to difliculties when that product is applied in the compounding of certain detergent compositions and particularly detergent compositions in bar form.

With the process of this invention the undesirable sodium chloride in the epoxidized product can be readily removed by means of a simple settling operation. Subsequent to the epoxidation reaction, which proceeds to substantial completeness, the epoxidized mixture is allowed to remain quiescent whereupon the aqueous phase of the epoxidized product, comprising sodium hydroxide solution containing dissolved sodium chloride, settles out of the epoxidized ether to form an aqueous seat, the epoxidized ether stratifying above this seat.

In carrying out this settling operation to a successful end, i.e. to the removal of substantially all of the sodium chloride from the epoxidized ether product, the concentration of sodium hydroxide is of great importance since the concentration of this solution determines the amount of sodium chloride which it will solubilize. Thus, if sodium hydroxide concentrations in excess of 50% are used, some of the sodium chloride will precipitate. The finely divided solid will tend to stabilize the aqueous-ether emulsion, making phase separation diflicult. If, on the other hand, the concentration of sodium hydroxide in the epoxidation reaction is less than about 25%, a decrease in completeness of the epoxidation will result.

The epoxidized ether product formed in accordance with the foregoing process comprises from about 10% to about 30% by weight of a glycidyl ether of the formula where X is either a hydroxyl or chloride radical.

It has now been discovered that the glycidyl ethers cannot be sulfonated in accordance with the recognized Streckerization reaction, i.e., through the use of sodium sulfite alone. This is particularly true of the dimer ether, the formula of which is set forth above. With these particular ethers a sulfonating medium comprising, in combination, sodium sulfite and sodium bi-sulfite must be used in order that the sulfonation of the compound can be successfully carried out. Although theoretical considerations involved are not to be considered limiting, it is believed that the presence of sodium sulfite in the sulfonating agent is necessary to Streckerize the chloride of the dimer and the presence of the bisulfite is necessary to sulfonate the epoxy groups of the monomer and dimer present.

As a matter of convenience, wherever herein the term Streckerization appears, sulfonation with alkali metal sulfite is indicated, whereas the term sulfonation connotes reaction of the glycidyl ether with a combination of alkali metal sulfite and bisulfite.

As has been pointed out hereinbefore, the sodium sulfite and sodium bisulfite in the sulfonating reagent are preferably proportioned to give a final pH in the range from about 5 to about 8. If the pH of the reacting mixture rises appreciably above 8, the sulfonation completeness begins to drop off rapidly. pH values below 5, on the other hand, offer slight additional advantage in terms of sulfonation completeness but introduce corrosion problems unless special equipment is utilized. Hence, as a practical matter, it is preferred that the pH of the reacting mixture and of the final sulfonated paste product be maintained in the range from about 5 to about 8.

It is desirable, of course that the sulfonation reaction be carried out to substantial completeness. Hence, as a practical matter, an amount of sodium sulfite-sodium bisulfite sulfonating agent equivalent to at least the stoichiometric amount needed to completely sulfonate the epoxidized ether product is normally used. However, and as pointed out hereinafter, with the present invention amounts well below the theoretical requirements may be utilized. In any event, the amount of sulfonating agent should generally be commensurate with maximum sulfonation completeness.

The sulfonation reaction can be carried out at moisture contents well below 50% and even as low as about 30%, presumably because of the greater solubility of the bisulfite. Moreover, it was unexpectedly found that, even in the presence of such relatively small amounts of water during the sulfonation reaction, the completeness of the sulfonation reaction was, on the average, higher than that obtained in practicing alkyl glyceryl chloro ether Streckerization under optimum conditions.

In carrying out the sulfonation of the glycidyl ethers care must be exercised so that the temperature does not become excessive. In the usual Streckerization reaction an induction period is normally encountered during which Streckerization does not proceed at an appreciable rate. Once Streckerization begins however, the exothermic nature of the reaction is sufiicient to cause an increase in temperature which, in'turn, accelerates the reaction. As a consequence, if it is desired to promote Streckerization through heating of the reactants, with a subsequent reduction in the length of the induction period, extreme care must be exercised in order that the exothermic nature of the reaction does not carry the temperature of the reactants to an extreme which would adversely affect them. Hence, as a general matter, it is not practical to heat the reactants to temperatures which will substantially reduce the induction period.

In order to avoid any adverse effects during the sulfonation reaction attributable to too high temperatures, it has been found that the addition of a small amount of an alkyl glyceryl ether sulfonate (paste seed), to the glycidyl ethers prior to contact with the sulfonating agents will effectively reduce the induction period and promote the sulfonation reaction. This is presumably attributable to the fact that a twophase system is involved in the sulfonation reaction, e.g. an ether phase and an aqueous sulfite phase. Consequently, intimate contact between these two phases is required before rapid reaction can occur. Because of poor interphase contact during the induction period the reaction is slow and it is only when sufiicient alkyl glyceryl ether sulfonate has been formed to promote good emulsification that adequate interphase contact is established with an attendant increase in the sulfonation reaction rate.

Sulfonation of the glycidyl ethers offers an additional advantage over the usual chloro ether Streckerization in that the temperature at which the sulfonation reaction will begin to proceed is considerably lower than that at which Streckerization will commence. For example, with about a 10% paste seed, chloroether Streckerization will begin at a temperature of about 340 F. but will proceed very slowly. With the glycidyl ethers, on the other hand, sulfonation will begin and proceed at a rapid and practical rate at temperatures as low as 300 g v F. Since the sulfonation and StreckeriZation reactions are of an exothermic nature, the lower starting temperature is extremely advantageous in avoiding overheating of the reaction mixture while sulfonation is progressing.

It has also been found that sulfonation of the glycidyl ether at the low moisture contents hereinbefore set forth offers a still further advantage in that the s-ulfite usage can be decreased to well below the theoretical requirements before sulfonation completeness is appreciably aifccted.

It is to be understood that although in the foregoing discussion (and in the following examples) only sodium sulfite and sodium bisulfite have been disclosed as the Streckerizing and/ or sulfonating agents, other alkali metal sulfites, such as potassium sulfite and bisulfite, also find ready application as sulfonating and/or Strec kerizing agents. Then too, if it is desired to have salts other than the sodium or potassium salts of the alkyl glyceryl ether s-ulfonate, such as for example, the calcium, magnesium, ammonium or alkylol substituted ammonium salts, the sodium salt, for example, can be passed over an ion exchange resin to replace the sodium ion with a hydrogen ion and the resulting acid neutralized with calcium or magnesium hydroxide, ammonia or alkylol substituted ammonia (alkylol amines).

In the following examples, in which all parts are expressed by weight, and which are meant to be illustrative only, the various expressions are defined as follows:

Percent C 2 C 66 h 23 1 The subscript denotes the number of carbon atoms in the alkyl chain.

C alcohol-the alcohol derived from fractionally distilling the alcohols made by the sodium reduction of coconut oil, the separated alcohol comprising about .97% alcohol containing 12 carbon atoms in the alkyl chain and having a molecular weight of about 186.

The sulfonation completeness expressed in terms of percent may be readily found from the following table which expresses the calculated Cat. SO /Extract ratio as a function of sulfonation completeness.

Sulfonation completeness Cat. 80;;/ Extract percent: ratio 0.38

Example 1.Two thousand parts of middle cut CN alcohol was mixed with 45.5 parts stannic chloride and the mixture was heated to 170 F. 1020 parts of epichlorohydrin was then added to this mixture while holding the temperature to a maximum of 220 F. After addition of all the epichlorohydrin the temperature of the mix was held at 220 F. for 15 minutes. Then, 1000 parts of water was added to the mixture and the resultant mixture was agitated and settled to separate the ether layer. The ether layer was subsequently distilled and 500 parts of the ether distilled was then treated with a solution of parts sodium hydroxide in 200 parts water at 195 F. for 3 hours. The resultant product was allowed to settle in order that the ether-containing phase and aqueous phase of the product would separate.

123 parts of the separated ether phase (the alkyl glycidyl ether) was then mixed Wilh 58.6 parts of Sodium bi-sulfite and 350 parts water andallowed to react for about 2 hours at 338 F. V

The resultant paste had a strong sulfur dioxide odor,

was gray in color (indicative of equipment corrosion),

had a pH of about 5.6 and a sulfonation completeness of about 55%.

Example 2.-2500 parts of alkyl glyceryl ether was prepared in accordance with the process of Example 1, utilizing C fatty alcohol and employing 1.1 moles of epichlorohydrin per mole of fatty alcohol and 0.3% of stannic chloride as a catalyst. This ether was then reacted with 1132 parts of 50% aqueous solution of sodium hydroxide at a temperature of F. for 2 hours.

250 parts of the epoxidized ether, 172 parts of potassium sulfite, and 425 parts of water were reacted at 375 F. for 1 hour, Resultant paste was dark, poor in sulfonation completeness and had a pH of 13.

Conversion of some of the potassium sulfite t'o potassium bisulfite through the addition of sulfuric acid gave the following results.

11,804 Added (Percent of J v Complete- Amount Required to Form pH Color tress Potassium Blsulflte) It is readily discernible from the foregoing that the application of a sulfite-bisulfite mixture for sulfonating the epoxidized ether, with the attendant decrease in ,pH, offers considerable advantage in sulfonation completeness as well as in product color.

Example 3. -6.75 parts of alkyl glyceryl chloroe'ther, prepared by reacting middle cut coconut alcohols with 12.5% excess epichlorohydrin in the presence of a stan-' nic chloride catalyst, was mixed with 3 parts of a 50% aqueous solution of sodium hydroxide and 3 parts of water. This mixture was allowed to react for 1 hour at a temperature of 180 F. The reaction product was their water washed to a pH of 7-8 and was dried and filtered. The resulting glycidyl ether had an analysis of 3.2% residual Cl and 30.6% Epi.

14.1 parts of this glycidyl ether was then mixed with 7.6 parts of sodium sulfite, 3 parts concentrated sulfuric acid (96% sulfuric acid) diluted with 12.9 parts of water; and 4 parts of alkyl glyceryl ether sulfonate paste (derived from middle cut CN alcohol and containing 58% water). The amount of sulfuric acid added was .calculated to be sufiicient to convert about 60% of the sodium sulfite to sodium bisulfite and thus afford a Sulfonating agent containing both sodium sulfiteand sodium bisulfite. During the sulfonation reaction the tempera ture of the sul-fonating mixture rose from 360 to 420f F. in 8 minutes. The resulting product had a Cat. $0. analysis of 10.7 and a hexane extract analysis of 9.5.

Utilizing the table set forth above, the apparent sulfonation completeness in the products of the foregoing reaction was in excess of 80%.

parts of a 50% aqueous solution of sodium, hydroxide and 3 parts of water. The reaction was allowed to pro- -7 grass at 170 F. for one hour. After the reaction had proceeded to substantial completeness 2 parts of water was added to the reaction mixture to dissolve the sodium chloride formed and allow separation of the phases.

16.9 parts of the epoxidized ether obtained from the foregoing reaction was mixed with 5.5 parts of sodium bisulfite, 2.2 parts of sodium sulfite, 4.4 parts of alkyl glyceryl ether sulfonate paste (derived from middle cut CN alcohol and containing 58% water) and 15 parts of water. This mixture was heated to a temperature of 330 F. to promote the sulfonation. After the sulfonation re action had begun the temperature of the reacting mixture rose to 420 Fin 7 minutes.

The resultant product had the following analysis: Cat. 80;, 12.6, unsulfonated 5.6, pH 5.2.

' Reference to the table set forth above indicates that the product had a sulfonation completeness in excess of 90%.

An alkyl glyceryl ether sulfonate, prepared in the foregoing manner, was utilized in the preparation of a detergent product in bar form. This barwhich had the approximate composition: 25% of the alkyl glyceryl ether sulfonate; 50% soap (the sodium salts of long chain fatty acids derived from coconut oil and tallow); 20% water; and minor ingredients and impuritieswas found to be eminently suitable for general toilet purposes.

The alkyl glyceryl ether sulfonate, prepared as above, was additionally used to prepare a liquid detergent product comprising in combination approximately 9% alkyl benzene sulfonate, 4% of the alkyl glyceryl ether sulfonate, 18% tetra-potassium pyrophosphate, 4% silicate solids, and 50% water, the remainder of the detergent household use.

Example 5.--l8.6 parts of the epoxidized ether prepared in accordance with Example 4 was mixed with 6.1 parts of sodium bisulfite, 2.4 parts of sodium sulfite, 12.5 parts of water and 4.4 parts of alkyl glyceryl ether sulfonate (derived from middle cut CN alcohol and containing 16% water). The mixture was heated to induce sulfonation and after sulfonation had begun, the temperature of the reacting mix was observed to rise to 430. F. in 18 minutes with no evidence of an induction period.

The resultant product had the following analysis: Cat. 50;, 16.5; unsulfonated 7.7; pH 6.95; NaCl 2.8.

The Cat. 50;, to unsulfonated ratio indicates that a sulfonation completeness in excess of 90% was obtained.

It is to be noted that in this example the overall water content was approximately 30% during the sulfonation reaction.

Example 6.-17.2 parts of epoxidized ether prepared in accordance with the process of Example 4 was mixed with 5.6 parts of sodium bisulfite, 2.2 parts of sodium sulfite, 16.9 parts of Water and 4.4 parts of alkyl glyceryl ether sulfonate. This mixture was then heated to promote sulfonation and it was noted that the sulfonation reaction commenced at a temperature of 275 F. and that the temperature of the reacting mixture rose to about 382 F. in 19 minutes.

The resulting product had the following analysis: Cat. S0 14.98; hexane extract 6.59; pH 6.7; NaCl 1.81.

Reference to the table set forth above will indicate that the sulfonation completeness was in excess of 90%.

A second sulfonation reaction was carried out utilizing the above constituents in the prescribed proportions except that the mixture was heated to 300 F. to initiate the sulfonation reaction and the reacting mixture rose to a temperature of 402 F. in minutes.

The resulting product had the following analysis: Cat. 80;, 15.1; hexane extract 6.77; pH 6.77; NaCl 2.33.

. The Cat. 50;, to extract ratio indicates that a sulfonation completeness in excess of 90% was obtained.

The overall water content was approximately 40% during the sulfonation reactions.

Example 7.-Sodium alkyl glyceryl ether prepared in accordance with the process outlined in Example 3 was reacted with a 40% aqueous solution of sodium hydroxide, the sodium hydroxide solution being present in an amount 50% in excess of the stoichiometric amount needed to epoxidize all the ether, in a pressure autoclave under the conditions and with the results expressed in the following table.

Time Tempera- Percent. Residual ture, F. Epi. Percent C1 The foregoing data are illustrative of the time-temperature relation in the epoxidation reaction of the pres ent process. With increasing temperatures the time for the reaction must be decreased in order to avoid excessive hydrolysis of the epoxidized ether product. Thus. epoxidation at temperatures of about 300 F. and even higher, where pressure equipment is used, are practicable if an appropriate adjustment is made in the total time for reaction.

Example 8.--Sodium alkyl glyceryl ether was prepared in accordance with the process outlined in Example 3 from a mixture of 34.2 parts of epichlorohydrin, 65.5 parts of middle cut coconut alcohol and 0.3 part of stannic chloride catalyst.

This ether, which had a chlorine content of 13.1% was then epoxidized under the conditions and with the results expressed in the following table.

Parts by Weight Per' Temp, Time, cent Residual F. Hr. Epi. Cl Ether NaOH H 0 The percent Epi and Residual Cl values are representative of substantially complete epoxidation and may be compared with theoretical values of about 32.1% epoxidc and about 2.4% Residual Cl calculated on the assumptions that complete epoxidation is obtained and that negligible hydrolysis of unepoxidizable chlorine occurs.

In the foregoing examples, individual alcohols having from about 10 to 20 carbon atoms, as well as mixtures thereof, and especially those mixtures derived from natural vegetable fats and oils, such as coconut oil, tallow, marine oils, and palm oil, can be substituted for the coconut middle cut alcohols to give substantially the same improved result. Also, other alkali metals may be substituted for sodium in the preceding examples with comparable results.

It can be seen from a comparison of Examples 1 and 2 with Examples 3, 4, 5 and 6 that the instant process offers considerable advantage in promoting sulfonation completeness and, in general, effectively accomplishes the objects of the invention.

Having thus described the invention, what is claimed 1. In the preparation of alkyl glyceryl ether sulfonates, the steps which comprise reacting a fatty alcohol having from about 10 to about 20 carbon atoms with an amount of epichlorohydrin at least 5% in excess of the molar amount required to form alkyl monochloroglyceryl ether and sufficient to form an alkyl glyceryl other product containing at least about 10% and not over 30% by weight of alkyl diglyceryl dichloro ether, treating the said product with an aqueous alkali metal hydroxide solution having a concentration of from about 25% to about 5 to epoxidize the said ether product, settling the resultant mixture to stratify the epoxidized ether and aqueous phases present, separating the stratified epoxidized ether product, and sulfonating the said epoxidized ether with an aqeous solution comprising in combination alkali metal sulfite and alkali metal bisulfite proportioned to give a final solution pH in the range from about to about 8, whereby alkyl glyceryl ether sulfonates having a low salt content are produced.

2. The process of claim 1 wherein the epoxidation reaction is carried out under atmospheric pressure at a emperature in the range from about 160 to about 200 3. The process of claim 1 wherein the sulfonat-ion is initiated at a temperature of about 275 F. by the addition of a small amount of alkyl glyceryl ether sulfonate as an emulsifier.

4. The process of claim 1 wherein the aqueous alkali metal hydroxide solution is present in an amount from 0% to about 50% in excess of the stoiehiometric amount needed to completely epoxidize all of the alkyl glyceryl chloro ethers present.

5. The process of claim 1 wherein the sulfonation is carried out under conditions such that the total moisture content of the final alkyl glyceryl ether sulfonate is about 40% by weight.

6. A composition of matter consisting essentially of a mixture of substantially inorganic-salt-free glycidyl ethers containing at least and not more than about 30% by weight of glycidyl ethers of the formula where R represents an alkyl radical of from about 10 to about 20 carbon atoms and X isselected from the group consisting of -Cl and -OH, the said mixture of glycidyl ethers being the substantially inorganic-salt-firee products obtained from reacting a fatty alcohol having from about 10 to about 20 carbon atoms with an amount of epichlorohydrin at least 5% in excess of the molar amount required to form alkyl monochloroglyceryl ether and sufficient to form a mixture of high molecular aliphatic chloroglyceryl ethers of the formula where n is an integer from 1 to 4, said chloroglyceryl ether mixture containing at least about 10% and not over 30% by weight of a high molecular aliphatic chloro glyceryl ether corresponding to the above formula where n=2, treating the said chloroglyceryl ether mixture with an aqueous alkali metal hydroxide solution having a concentration of from about 25% to about to epoxidize the said chloroglyceryl ether mixture, thereby forming the corresponding glycidyl ethers, settling the resultant mixture to stratify the epoxidized ether and aqueous phases present, and separating the stratified epoxidized ether mixture.

References Cited in the file of this patent UNITED STATES PATENTS 2,094,489 Hueter et a1 Sept. 28, 1937 2,810,747 Sexton et a1. Oct. 22, 1957 FOREIGN PATENTS 751,244 Great Britain June 27, 1956 

6. A COMPOSITION OF MATTER CONSISTING ESSENTIALLY OF A MIXTURE OF SUBSTANTIALLY INORGANIC-SALT-FREE GLYCIDYL ETHERS CONTAINING AT LEAST 10% AND NOT MORE THAN ABOUT 30% BY WEIGHT OF GLYCIDYL ETHERS OF THE FORMULA 